Interstaple Dithiol Cross-Linking in Au25(SR)18Nanomolecules: A Combined Mass Spectrometric and Computational Study,Journal of the American Chemical Society

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Interstaple Dithiol Cross-Linking in Au25(SR)18Nanomolecules: A Combined Mass Spectrometric and Computational Study
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2011-12-21 , DOI: 10.1021/ja206436x
Vijay Reddy Jupally ₁ , Rajesh Kota ₁ , Eric Van Dornshuld ₁ , Daniell L. Mattern ₁ , Gregory S. Tschumper ₁ , De-en Jiang ₂ , Amala Dass ₁

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A systematic study of cross-linking chemistry of the Au(25)(SR)(18) nanomolecule by dithiols of varying chain length, HS-(CH(2))(n)-SH where n = 2, 3, 4, 5, and 6, is presented here. Monothiolated Au(25) has six [RSAuSRAuSR] staple motifs on its surface, and MALDI mass spectrometry data of the ligand exchanged clusters show that propane (C3) and butane (C4) dithiols have ideal chain lengths for interstaple cross-linking and that up to six C3 or C4 dithiols can be facilely exchanged onto the cluster surface. Propanedithiol predominately exchanges with two monothiols at a time, making cross-linking bridges, while butanedithiol can exchange with either one or two monothiols at a time. The extent of cross-linking can be controlled by the Au(25)(SR)(18) to dithiol ratio, the reaction time of ligand exchange, or the addition of a hydrophobic tail to the dithiol. MALDI MS suggests that during ethane (C2) dithiol exchange, two ethanedithiols become connected by a disulfide bond; this result is supported by density functional theory (DFT) prediction of the optimal chain length for the intrastaple coupling. Both optical absorption spectroscopy and DFT computations show that the electronic structure of the Au(25) nanomolecule retains its main features after exchange of up to eight monothiol ligands.

中文翻译：

Au25(SR)18 纳米分子中的间二硫醇交联：一项结合质谱和计算的研究

通过不同链长的二硫醇对 Au(25)(SR)(18) 纳米分子的交联化学进行系统研究，HS-(CH(2))(n)-SH 其中 n = 2, 3, 4, 5 和 6 在这里介绍。Monothiolated Au(25) 在其表面有六个 [RSAuSRAuSR] 主要基序，配体交换簇的 MALDI 质谱数据表明丙烷 (C3) 和丁烷 (C4) 二硫醇具有理想的链长，用于订书钉间交联，并且到六个 C3 或 C4 二硫醇可以很容易地交换到簇表面。丙二硫醇主要一次与两个单硫醇交换，形成交联桥，而丁二硫醇一次可以与一个或两个单硫醇交换。交联的程度可以通过 Au(25)(SR)(18) 与二硫醇的比例、配体交换的反应时间、或向二硫醇添加疏水尾。MALDI MS 表明，在乙烷 (C2) 二硫醇交换期间，两个乙二硫醇通过二硫键连接；这一结果得到了密度泛函理论 (DFT) 预测的最佳订书钉内偶联链长的支持。光吸收光谱和 DFT 计算表明 Au(25) 纳米分子的电子结构在交换多达八个单硫醇配体后仍保留其主要特征。

更新日期：2011-12-21

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